Rubberlike materials and an unsaturated hydrocarbon oil



. porati'ng Patented Mar. 2, 1954 RUBBERLIKE MATERIALS AND AN UNSATU-RATED HYDROCARBON OIL Herman S. Bloch, Chicago, Ill., asslgnor toUniversal Oil Products Company, Chicago, Ill.,,a

corporation of Delaware Serial No. 300,974

No Drawing. Application July 25, 1952.

20 Claims. 2611-43-6) This application is a continuation-in-part of mycopending application serial No. 36,262, died June 30, 1948, nowPatentNo. 2,615,856, October This invention relates to a process for producingand employing a hydrocarbon material useful as a plasticizer and.extender for rubber. More specifically. this invention is concerned withthe production of vulcanized rubber-like composites comprisingessentially a rubber, sulfur, and a hydrocarbon formed by treatingaliphatic hydrocarbons with hydrogen fluoride.

An object of this invention is the production of a rubber plasticlzerfrom the hydrogen fluoride catalyst layer used in conversion reactionsof aliphatic hydrocarbons.

Another object of this invention is to produce a plasticizer andextender for rubber by reacting at least one aliphatic hydrocarbonselected from the group consisting of isoparafllnic and oleflnichydrocarbons in the presence of liquid hydrogen fluoride.

A further object of this invention is to plasticize a rubber selectedfrom the group consisting of natural rubber and synthetic rubber byincortherein a hydrocarbon material boiling above about 150 C. andobtained from a hydrogen fluoride layer which has catalyzed thealkylation of an isoparafllnic hydrocarbon by an oleflnic hydrocarbon.

A still further object of this invention is to plasticize a rubber byincorporating therein a hydrocarbon mixture derived from materialboiling above about 150 C. obtained by reacting an oleflnlc hydrocarbonhaving at least three carbon atoms per molecule in the presence ofhydrogen fluoride containing less than about by weight of water at atemperature of from about 0 to about 150 C.

One specific embodiment of this invention comprises a process forplasticizing a rubber selected from the group consisting ofpolybutadiene, butadiene-amethylstyrene copolymers, butadiene-vinyltoluene copolymers, butadiene-amethylvinyltoluene copolymers,isoprenestyrene copolymers, isoprene a methylstyrene copolymers,isoprenevinyltoluene copolymers, isoprenea-methylvinyltoluene.coplymers, isopreneisobutylene copolymers,.isoprene-acrylonitrilecopolymers, conjugated hexadiene-styrene copolymers,

conjugated hexadiene cmethylstyrene copolymers, conjugatedhexadiene-vinyltoluene copolymers, conjugatedhexadiene-u-methylvinyltoluenc copolymers, conjugatedhexadiene-isobutylone copolymers, and conjugated hexadieneacrylonitrilecopolymers, which comprises incorporating therein a plasticizer selectedfrom the group consisting of (1) a polyolefinic cyclic hydrocarbonresidue containing conjugated oleflnic unsaturation and produced byreacting in the presence of liquid hydrogen fluoride at a temperature offrom about 0 to about 150 C. at least one aliphatic hydrocarbon selectedfrom the group consisting of isoparaflinic and oleflnic hydrocarbons,separating the resultant reaction products into a hydrocarbon layer anda hydrogen fluoride layer,- recovering a substantially fluorine-freehydrocarbon material from said hydrogen fluoride layer, and removingfrom said duced by reacting an oleflnic hydrocarbon having at least 3carbon atoms per molecule with liquid hydrogen fluoride at a temperatureof from about 0 to about C.

For some time it has been recognized that the workability of naturalrubber and synthetic polymers usable as rubber substitutes-is improvedby plasticizing and softening these rubber-like materials beforesubjecting them to milling. molding, and vulcanizing operations.Synthetic-polymers and natural rubber have been plasticized byaddingthereto substances such as oils. fats, waxes and the like,including tars, high molecular weight hydrocarbons recovered fromsulfuric acid-hydrocarbon sludges, solvent extracts of petroleum oils,residues from the clay-treating of petroleum fractions and the like. Useof the aforementioned plasticizers causes the rubberlike materials toflow more easily and accordingly to process more advantageously inmilling and in molding operations. However, many of the previously usedplasticizers do not cause sufllcient plasticization of the rubberymaterials and sometimes give undesirable properties to the finishedproducts. For example, some plasticizers are objectionable in odor,color, or in their influence upon the tensile strength and elongation ofthe flnished rubber product. i

A method of the prior art relates to treating cracked gasoline with 0.1to 5% of its weight of substantially anhydrous hydrogen fluoride toremove readily oxidizable and polymerizable constituents which tend toreadily form gum on storage without removing any substantial proportionof monooleflns." As this treatment removed from the cracked gasolineonly constituents more easily polymerizable than the monos oleflns, itis evident that the resultant polymerized constituents were different inchemical composition from my plasticizer oil which is recovered from aconiunct polymer derived from a monooleflnic or isoparaflinichydrocarbon which has been contacted with from to 100% and preferablyfrom about 80 to about 65% of its weight of liquid hydrogen fluoride.

I have obtained a is useful, not only as a plasticize but also as anextender in natural rubber and synthetic rubbers. The term "extender" asherein employed refers to a substance which may be admixed withnathydrogen fluoride layer containinghydrocarbon product which 1 4include certain amounts of a more unsaturated v oleflnic hydrocarbon,namely, a dienic hydrocarbon as, for example, butadiene-l, 3, isoprene,cyclopentadiene and the like or an acetylenic hydrocarbon. These moreunsaturated hydrocarbons comprising dienes and acetylenes are generallyused in admixture with monooleflnic hydrocarbons to form highlyunsaturated plasticizers.

Other aliphatic hydrocarbons utilizable in this process for producing ahydrocarbon piasticizer comprise isoparaflinic hydrocarbons orhydrocarbon mixtures containing substantial amounts of isoparafiinichydrocarbons, preferably together with oleflnic hydrocarbons. Theisoparaillnic hydrocarbons may vary in molecular weight but it isfrequently advantageous to employ a mixture of branched-chain parafllnichydrocarbons boilural rubber or synthetic rubber to increase the volumeand weight of the finished rubber-like material without affectingappreciably the desirable characteristics of the rubber-like material.Accordingly, should prferably covulcanize with the natural rubber,synthetic rubber, or mixtures of these materials.

Monooleflnic hydrocarbons utilizable in producing the plasticizeremployed in this process have at least three carbon comprise propylene,the butylenes, pentenes, hexenes, heptenes, octenes, and higher boilingmonoolefinic hydrocarbons. Of these materials, propylene has been foundto require the higher portions of the catalyst: olefin ratios and of thetemperature range cited for its satisfactory reaction, while the higheroleflns undergo reaction even in the lower portions of the ranges ofthese variables. A preferred source of monooleflnic hydrocarbon ispolymer gasoline for example, by polymerizing propylene and butylenes ormixtures thereof in the presence of solid phosphoric acid catalyst,which is a calcined composite of a phosphoric acid and a siliceouscarrier such as diatomaceous earth, also called kieselguhr. Fractions ofcracked gasoline containing substantial amounts of oleflns andrelatively small proportions of aromatic hydrocarbons are also suitablecharging stocks. These the material employed as extender,

atoms per molecule and mg above about 150 C. For example, a materialrich in higher boiling isoparaflinic and other branched-chain parafllnichydrocarbons may comprise'the higher boiling fractions of productsformed by the alkylation of an isoparafllnic hydrocarbon with amonooleflnichydrocarbon to form aviation gasoline. Such hydrocarbonsboiling higher than aviation gasoline may be used as such or selectedfractions thereof, such as the 150-200 C. or 200-450 C. fraction, may bereacted with hydrogen fluoride at a temperature of from about 30 toabout 150 C. to form a still higher boiling hydrocarbon material, thelatter utilizable as a plasticizer. The 'isoparafllns require a somewhathigher reaction temperature than olenns, since the former must first becracked to oleflnic fragments before conlunct polymerization can takeplace.

Hydroyen fluoride catalysts process and also referred to as employed inthis hydrofluoric acid contain a major proportion by weight of hydrogenwhich is formed, 40

gasoline charging stocks may also contain certain amounts of paraflinicand naphthenlc hydrocarbons some of which may be alkylated during thepolymerization treatment. C3 and C4 fractions recovered from theproducts of cracking and a C4 fraction recovered from butanedehydrogenation and containing mainly butylenes and normal butane withrelatively little isobutane are also good charging stocks for thisprocess.

Olefinic hydrocarbons having more than three carbon atoms per moleculeare more desirable as charging stocks than propylene because of theincreased yield of both saturated and unsaturated liquid products andimproved properties of the products obtained from these preferredcharging because of their greater ease stocks, as well as of reaction.About the same quantity and quality of plasticizer oil are obtained whencharging any of the oleflns having from 4 to about 12 carbon atoms permolecule. The different monoolefins having at least four carbon atomsper moleg cule appear to be mutually interconvertible by polymerizationand depolymerization reactions at the conditions specified for thisprocess.

Other unsaturated hydrocarbons which may be fluoride and generally maycontain as much as 10% by weight of water, although the titratableacidity of the catalyst-layer may be less than because of the presencetherein of dissolved organic compounds including highly unsaturatedmaterials which are described more completely hereinafter. The catalystpreferred in this process is substantially anhydrous hydrogen fluoride,that is, hydrogen fluoride, or the hydrogen fluoride of commerce, of98+% purity.

The process for producing the plasticizer oil comprises essentiallyreacting an aliphatic hydrocarbon selected from the members of the groupconsisting of isoparaiflnic and oleiinic hydrocarbons in the presence ofliquid hydrofluoric acid at conjunct polymerization conditions whichinclude a temperature of from about 0 to about C. and a pressuresufficient to maintain the reactants and hydrogen fluoride catalyst insubstantially liquid phase, separating the resultant 1 upper saturatedhydrocarbon layer from the lower hydrogen fluoride sludge layer, andthen decomposing the hydrogen fluoride sludge layer by water hydrolysis,by heating or by another suitable method to recover the plasticizer oiltherefrom. The weight ratio of hydrogen fluoride catalyst to aliphatichydrocarbon charging stock, that is, the isoparamnic, oleflnic, orcombined mixture of isoparafflnic and oleflnic hydrocarbons will varyfrom about 0.1 to about 10. When the hydrogen fluoride to aliphatichydrocarbon weight ratio is less than about 0.1,,it is necessary torecycle excessive amounts to the hydrocarbons in order to obtain goodconversion, while increases in this ratio above about 10 eifect verylittle furused in producing the plasticizer of this process 75 therincrease in yield of the desired reaction products but such insreasedratio of hydrogen fluoride to the total isoparafllnic and oleflnichydrocarbons does decrease the capacity of the reactor andother treatingequipment.

When isoparafflnic, oleflnic, and mixtures of isoparafllnic and olefinichydrocarbons are contacted with hydrofluoric less than about by weightof water, a complex series of reactions occurs which is herein referredto in the aggregate as a coniunct polymerization reaction." Thisconjunct polymerization reaction comprises an initial polymerization andcondensation reaction between the hydrocarbons present in the reactionmixture and as the reaction progresses further, cyclization andisomerization of the polymers occur, accompanied by a hydrogen transferreaction between the various hydrocarbons and conjunct polymers presentin. the reaction mixture whereby part of the conjunct polymers areconverted into saturated hydrocarbons by virtue of the hydrogen transferat the expense of other components which are converted into highlyunsaturated hydrocarbons containing on an average of from about 2 toabout 4 double bonds per molecule of which from about 40 to about 70%are con- Jugated. The resulting unsaturated conjunct polymerscomprisinga series of high molecular weight polyoleflnic cyclichydrocarbons become attached by weak chemical bonds to the hydrogenfluoride catalyst to form a sludge-like complex addition product inwhich fluorine is not, however, organically bound, since it can besubstantially all recovered by treatment of the complex with water orwith cold aqueous alkali. The saturated hydrocarbon conjunct polymersform a hydrogen fluoride-insoluble phase which upon settling of thereaction mixture separates as a distinct upper layer which is separatedreadily from the lower hydrogen fluoride layer in which the highlyunsaturated polyolefinic cyclic hydrocarbons are contained.

It is of interest to note that in this type ofcopolymerization, in whichhydrogen transfer occurs, the product recovered from the sludge orcatalyst layer has a higher molecular weight than the charge stock, andis generally more unsaturated than the charge stock.

As the saturated hydrocarbons of the upper layer boil over about thesame range of temperature as do the unsaturated plasticizer oilconstituents recoverable from the hydrogen fluoride lower layer and assmall amounts of the saturated hydrocarbons are entrained or mixed withthe hydrogen fluoride lower layer, it is advisable to extract thehydrogen fluoride lower layer with a low boiling saturated hydrocarbon,preferably a paraflln having from 3 to about 8 carbon atoms permolecule, before hydrolyzing, or otherwise decomposing, the hydrogenfluoride lower layer to recover the unsaturated drying oil therefrom.From the lower layer, the hydrogen fluoride and plasticizer oilfractions are then separated by suitable means, for example, the lowerlayer may be added to water or ice whereby the hydrogen fluoride isdissolved in water to form an aqueous solution from which theplasticizer oil separates as an upper layer. Also the lower layer may besubjected to flash distillation to vaporize the hydrogen fluoride fromthe higher boiling highly unsaturated plasticizer oil. When the lowerlayer is separated by distillation methods, the recovered hydrogenfluoride is suitable for recycling to the process to acid catalystcontaining 6 eflect reaction of additional quantities of chargedmonooleflnic hydrocarbons.

Passage of inert gas, such as nitrogen, hydrogen, methane, ethane,carbon dioxide, and the like through the distillation system in whichthe hydrogen fluoride is being separated, assists in the recovery of thehighly unsaturated plasticizer oil. Separation of hydrogen fluoride fromthe plasticizer oil present in the lower layer is also assisted bycarrying out the flash distillation of said lower layer in a towercontaining catalytic packing material formed from graphitized carbon orfrom a metal selected from the members of the group consisting ofaluminum, copper, cobalt, lead, cadmium, and an alloy of copper, such asbrass, and preferably in the presence of an inert carrier gas to assistin removing the librated hydrogen fluoride.

Another method of decomposing the hydrogen fluoride-plasticizer oilmixture of the lower layer formed by the conjunct polymerization ofoleflnic hydrocarbons in the presence of hydrogen fluoride, is tointroduce the lower. layer or sludge into an inert liquid, such as aparaflinic hydrocarbon contained in a decomposition 'zone and maintainedat a temperature near its boiling point. The decomposition zone orreactor tower may contain a catalytic packing material in the liquidzone of this reactor tower and an inert gas may also be passedtherethrough. Hydrogen fluoride so liberated is vaporized, condensed,

and conducted to storage while the inert liquid containing thedissolved, highly unsaturated plasticizer oil is withdrawn from thedecomposition zone, either intermittently or continuously, and replacedby fresh liquid. This liquid should be readily separable from theplasticizer oil dissolved therein, and it should also be relativelyinert to the hydrogen fluoride sludge and to the products of thedecomposition of the sludge. If a parafiinic naphtha is employed, itsnormal boiling point should be from about to C., so that it may beseparated by fractional distillation from the plasticizer oil whichboils generally from about 150 to about 450 0.

Another source of rubber plasticizer is the hydrogen fluoride catalystlayer which is recovered from an alkylation process in which aviationgasoline is formed by reacting an isoparafflnic hydrocarbon with amonooleflnic hydrocarbon such as a butylene or normally liquidmonoleflnic hydrocarbon. When such an alkylation process is conductedfor some time in the presence of a hydrogen fluoride catalyst, asubstantial proportion of organic material accumulates in the hydrogenfluoride catalyst layer and may be recovered therefrom by suitablemeans. For example, the used hydrogen fluoride catalyst may be subjectedto fractional distillation to sep-- arate therefrom hydrogen fluorideand leave as a residue a relatively high boiling hydrocarbon material.The organic material may also be separated from the used catalyst withwater whereby a hydrocarbon layer separates from the aqueous hydrogenfluoride. The resultant hydrocarbon material may' be used as such as arubber plasticizer, but I prefer to subject it to fractionaldistillation to remove therefrom the relatively low boiling hydrocarbonsso as to recover organic material of higher molecular weight frequentlyhaving the characteristics of a resin which I have found to be suitablefor mixing with natural rubber and various synthetic rubbers.

Study of the ultraviolet and infrared absorptlon spectra and otherproperties oi plasticiser oil iractions iormed irom polymer gasoline andboiling irom about 150 to about 200 C., shows that these hydrocarbonsare nonaromatic and that most oi them contain a pair oi coniugateddouble bonds with one of these double bonds in a ring oi five carbonatoms and the other double bond in an alkenyl side chain. Thus acyclopentane ring may be combined with a methylene group or a vinylgroup. However, some oi the plasticizer oil hydrocarbons which contain acyclopentenyl ring also contain more than two substituent groups buteach oi these groups is highly substituted. The higher boiling iractionsoi this plasticizer oil boiling up to about 450 0. contain nonaromatic,polycyclic, polyenic hydrocarbons which are generally bicyclic. In bothmonocyclic and polycyclic hydrocarbons the five-carbon atom ringportions oi the molecules are combined with at least two alkyl groups ortwo unsaturated aliphatic groups. The data obtained on these iractionsindicate that one oi the double bonds comprised by the coniugated dienesystems oi the plasticizer oil is within 9.

five-carbon atom ring and is in an alkenyl or alkapolyenyl substituent.Alkapolyneyl groups that may be present are highly branched and containisolated unsaturation as well as conjugated unstauration. Some oithetypical hydrocarbons contained in the plasticizer oil mixtures soproduced irom polymer gasoline are represented structurally by theiollowing iormula:

wherein the radicals R to R" are selected irom the group constisting oihydrogen and alkyl, alkenyl and alkapolyenyl hydrocarbon radicals, atleast two oi the substituents R to R" are hydrocarbon radicals, and notmore than two oi the groups R to R represent hydrogen.

Other constituents oi the plasticizer oil iormed from polymer gasolineare believed to have structures that may be represented by the iormula:

covered irom suliuric acid sludges recovered during petroleum refiningand described as rubber compounding agents or plasticizers. Diiierencesobserved in the ultraviolet and infrared absorption spectra of thesetypes oi plasticizer oils are given in Table 1. In order to interpretthe other double bond than two oi the substitu- 8 the results oi theultraviolet absorption spectra, use is made oi the specific extinctioncoemcient indicated in the table as E. The term "specific extinctioncoefficient is defined by the iollowing equation:

where Io=intensity of incident light (0811 illled with isooctane)I=intensity oi transmitted light (cell filled with solution oiplasticizers in lac-octane solvent.) C=concentration oi plasticizer incell in grams per liter L=len th oi cell path in centimeters.

TABLI 1 Ultraviolet and infrared absorption spectra of hydrocarbonplasticizers Plmtieizer recovered Plasticizer of Example from petroleumhydroboiling above 320 C. I carbon-suliurlc acid sludge Ultravioletabsorption spectra:

x-u 250 m 230 m. E 31. .99. X-a 58 m- Absorption due Dominant absorptionalmost entirely to is that ol aromatic I nonaromatic concompounds.

iugated dioleiln. Infrared absorp- There is compara- There iscomparatively tion spectra. tively weak absorpstrong absorption tlonwith generally I with generally broad sharp bands, and bands, some ofwhich evidence of the comare assignable to arw plete lack of aromaticcompounds. matic compounds.

The data on the ultraviolet absorption given in Table 1 show that theplasticizer oi this process has a single absorption maximum at a wavelength of 250 um while the plasticizer recovered from suliuric acidpetroleum hydrocarbon sludge has two ultraviolet absorption maxima,namely, at 230 m and 258 m Accordingly. from these data it is concludedthat the predominant ultraviolet absorption originated in these twoplasticizers in entirely different types of compounds. Ultravioletabsorption observed in the plasticizer of my process is due tononaromatic conjugated diolefln compounds while that obtained on theplasticizer recovered irom petroleum hydrocarhon-sulfuric acid sludge isdue to aromatic compounds.

The unsaturated polycyclic hydrocarbon plasticizers of my process alsodifler in many other ways from the unsaturated hydrocarbon plasticizersrecovered from sulfuric acid refinery sludges. These two types ofplasticizers difler in the types oi hydrocarbons present therein, thepercentages oi carbon and hydrogen, the molecular weights, and thedegrees oi unsaturation, as indicated by the comparative results give inTable 2.

TAIL! 2 Physical and chemical properties of hydrocarbon plasticizersColumn No 1 z A plasticiw' I recovered Platicizer of Example 1 frompetroleum hydroboiling above 330 C. carbon-sulfuric acid sludge (CH,1.73) 86H, 1.33). Formula C 28.4; H, 49.2 (Am) 24.9;11, 33.2 (An). m-Hu-n (AVJ Carp-1046K)- s: Percent Carbon 87.4 90. Percent Hydrogen 10.Mel. Wt 90 soc-1,000 (Av. 400). S ctures Polycyclic aromatics. DryingProperties Nondrying. Iodine No Bromine No... 166... (-38). MaleicAnhydrlde Value 56 Acid No 0 0. Oleflnic Double Bonds per Molecule:

Total (based on-bromine number)- 4 2. conlugatnd 1.7 olor (Reddlshyellow l7 Gardner).. Red-Brown.

1 These data are taken also from the article by Fritz Rustler and VilmaMehner India Rubber April 942 1 Equiv. oi Br No. I Equiv. oi Iodine No.

Worldl, August 1, 1941, pp. 47-51 and the article by L. Bornstein andThe plasticizer oil of the present process is a clude average brominenumbers of from about 120 to about 200; average number of double bondsper molecule of more than 2 and less than 5;

densities of about 0.85 to about 0.95; specific dispersions of about 125to about 175 (but usually below about 145); specific refractions ofabout 0.327 to about 0.335, and carbon to hydrogen atomic ratios 'closeto 1:1.7. Y

The relatively high molecular weight hydrocarbons which are so formed bytreating an r. Rostler, Modern Plastics,

' rubber-plasticizer composition is contained within the amount ofplasticizer that is added to When such a composite of unsaturatedhydrocarbon mixture and sulfur is heated to form a aliphatic hydrocarbonor aliphatic hydrocarbon J mixture with liquid hydrogen fluoride arehighly unsaturated and are covulcanizable with rubber I have found alsothat these unsaturated hydrocarbon materials will dissolve or react withat least 40% by weight of sulfur, forming products which range fromviscous oils to hard brittle solids. depending upon the sulfur content.

Mixtures of the cyclic polyenic plasticizer with sulfur react onlysluggishly at 150 C. and somewhat more readily at 200 C., but at 240 0.,the reaction is rapid and smooth. I

In general, a composite of a sulfur-vulcanizable rubber and my highlyunsaturated plasticizer requires a larger amount of sulfur forvulcanization than that used heretofore with rubber compounding mixturescontaining no plasticizer or containing a plasticizer of the prior artsuch as those derivatives from sulfuric acid sludges recovered from thetreatment of hydrocarbons. The amount of additional sulfur preferred (inexcess over the amount normally used with the rubber) is approximately 1part sulfur per every viscous fluid, and the latter is admixed withnatural rubber or synthetic rubber, the sulfur is dispersed readily anduniformily throughout the mass of rubber-like material. Inadditlon tothis advantage of aiding in the mixing of sulfur with rubber, theunsaturated hydrocarbonaceous material described above also has a 10parts plasticizer added to each 100 parts of rate of sulfur toplasticizer may be readily ad- Justed so that all of the sulfur requiredby the softening and plasticizing effect to make the rubber orrubber-like material more workable in rubber treating equipment. I

The plasticizer and extender referred to herein may be applied to anelastomer selected from the group comprising natural rubbers andsynthetic rubber-like polymers comprising diene polymers and copolymersof dienes with monooleflnic monomers. These various elastomers includenot only natural rubber and poly-butadiene, but also copolymers ofbutadiene with at least one member selected from the group ofmonoolefinic monomers consisting of styrene. a methylstyrene,vinyltoluenes, a methylvinyltoluenes, isobutylene, and acrylonitrile;copolymers of isoprene with at least one member of the group ofmonoolefinic monomers consisting of styrene, a-metlrwlstyrene.vinyltoluene, amethylvinyltoluene, isobutylene, and acrylonitrile; andcopolymers ofconjugated hexadienes with at least one member of the groupof monoolefinic monomers consisting of styrene, methylstyrene,vinyltoluene, o-methylvinyltoluene, isobutylene, and acrylonitrile. fthe various hexadienes, 2-methyl-1,3-pentadiene, 2,3-dimethy1-1,3-butadiene, and 1,3-hexadiene are most preferable. However, nointention to exclude other polymerizable conjugated hexadienes is meanthereby. The term a rubber is employed in this specification and in theclaims in a general sense to include caoutchouc, reclaimed rubber,balata, gutta percha, rubber isomers, and like products whether or notadmixed with fillers, pigments, vulcanizing or accelerating agents. Thisproduct may also be used in the reclaiming of vulcanized rubber in whichcase the plastioizer is not separated from the reclaimed rubber but bothmaterials are utilized in admixture.

The following examples are given to illustrate the character of resultsobtained by the use of specific embodiments of the present process,although the data presented are not introduced with the intention ofunduly restricting the generally broad scope of the invention.

"EXAMPLE I During a period of 94.5 hours, a total of 109 kgs. of polymergasoline was contacted with 35.6 kgs. of hydrogen fluoride at atemperature of 78 C. and at a pressure of 10.7 atmospheres. During thisrun, the charging rates of polymer gasoline and hydrogen fluoride were1610 and 381 cc. per hour, respectively, through a reactor of 1300 cc.capacity. The ratio of the volume of polymer gasoline to the hydrogenfluoride was thus 4.2. The average time during which the polymergasoline was in contact with the hydrogen fluoride was about 39 minutes.The reaction consisted of 90.! kg. of an upper hydrocarbon layer and44.3 kg. of a hydrogen fluoride layer, the latter containing someorganic compounds. The hydrogen fluoride layer'on treatment with icewater followed by washing of the separated oil with caustic sodasolution and filtering through a column of soda-lime and anhydrousbarium oxide yielded 16.! kg. of a clear oil which gave a neutralreaction when shaken with water and an indicator and was substantiallyfluorine-free. This hydrocarbon oil had the following properties:

Bromine number 181 Molecular weight 290 No. double bonds/moi. (by Br.No.) 3.3 No. conjugated double bonds/moi 1.9 Gardner color 11-12 Thehydrocarbon oil mentioned above was then distilled to remove the lowerboiling hydrocarbone, leaving in the still the higher boiling 50% of thehydrocarbon oil. The material remaining Molecular weight .i 390. Doublebonds/mol. (by Br. No.) 4. No.con:|ugated double bonds/incl- 1.7.

The plasticizer prepared as above described was then compounded with apolybutadiene p lymixture so obtained 12 mer, a butadiene-vinyl toluenecopolymer. an isoprene-isobutylene copolymer, an isoprene-styrenecopolymer, and an isoprene-vinyl toluene copolymer according to thefollowing standard formula: g. of polymer or copolymer, 50 g. of carbonblack (Kosmobile 7'1), 5 g. of zinc oxide, 1.5 g. ofmercaptobenzothiazole, 20g. of plastlcizer, and sulfur, the latter addedin amounts of 2, 3, 4, or 5 grams in separate tests. In case of theisoprene-isobutylene copolymer formulation, 1.0 g. oi tetramethylthiuram monosulflde was used as the accelerator. The composites preparedaccording to this test formula were then vulcanized at C. for 90minutes. The results of these tests are presented in the followingtable:

TABLE 1 Properties of vulcanized rubber containing 20% of plasticizerTensile Modulus Parts Sulfurll00 Parts Rubber Strength at 300%Elongation at break Elongation Polybutadiene:

0 0 0 0 o i u 0 0 a. o E 4. 0 0 5 c +-superior. I O-average. --lnferior.

EXAM? LE 11 A mixture of hydrocarbons recovered from a hydrogen fluoridecatalyst which had been used in a commercial plant in which isobutanewas alkylated with butylenes in the presence of hydrogen fluoridecatalyst was diluted with an equal volume of petroleum'ether, washed,and the hydrogen fluoride-free hydrocarbon material recovered.Properties of the recovered hydrocarbon material are as follows:

114' 0.95 Bromine number 101 Acid number 0.4 Viscosity (25 C.) poises3,350 Molecular weight 3'19 Diene value 8.7 Coniugated double bonds/mol0.28 Color (Gardner) 18 The above mentioned hydrocarbon mixture was thenused as a plasticizer in the standard test formula referred to inExample 1. The results of these tests are presented in the followingtable:

13 Test: 2 Properties of vulcanized rubber containing 20% of plasticizerTensile Modulus PartsSullur/IOOPm-tsRubber Strength at300% Elongation atbreak Elongation Polybutadiene:

0 s i i 0 0 s t I o I (T-superior. -a e e. Mitt.

EXANIPIE III A highly aromatic hydrocarbon was recovered from sulfuricacid sludge formed during the treatment of lubricating oil with sulfuricacid. This aromatic sludge oil was used as a plasticizer and compoundedwith an isoprene-styrene copolymer in the following test formula: 100 g.of isoprenestyrene copolymer, 50 g. of carbon black, 5 g. of zinc oxide,1.5 g. of mercaptobenzothiazole, g. of plasticizer, and 5 g. of sulfur.The sample was then vulcanized at 140 C. for 90 minutes. In thefollowing table, a comparison of the properties of the thusly producedrubber versus the properties of similar rubbers prepared with theplasticizers of Examples I and II is given:

From the results given in Table 3, it is seen that vulcanizedisoprene-styrene rubberof approximately the same tensile strength butgreater elongation was produced when using the plasticizer of Example Ithan when a plasticizer recovered from lubricating oil-sulfuric acidsludge was tested similarly. The vulcanized isoprenestyrene rubber ofExample 11 was superior in tensile strength and elongation to thatcontaining plasticizer recovered from lubricating oil-sulfuric acidsludge. For special uses in which a'partially cured (vulcanized) rubberis desirable (for-example, a flexible material for shoe soles) theplasticizers of Examples I and II have specific advantages over theplasticizer recovered from the lubricating oil-sulfuric acid sludge.

polymers, conjugated hexadiene-styrene copolymers, conjugatedhexadiene-a-methylstyrene copolymers, conjugated hexadiene-vmyltoluenecopolymers, conjugated hexadiene-a-methylvinyltoluene copolymers,conjugated hexadiene-iscbutylene copolymers, and conjugated hexadieneacrylonitrile copolymers, and a plasticizer selected from the groupconsisting of: (1) an unsaturated polycyclic hydrocarbon residuecontaining conjugated olefinic unsaturation and produced by reacting inthe presence of liquid hydrogen fluoride at a temperature of from about0 to about C. at least one aliphatic hydrocarbon selected from the groupconsisting of isoparamnic and oleflnic hydrocarbons, separating theresultant reaction products into a hydrocarbon layer and a hydrogenfluoride layer, recovering a substantially fluorine-free hydrocarbonmaterial from said hydrogen fluoride layer, and removing from saidlast-named material the hydrocarbons boiling below about 150 C. to leavesaid residue,

and (2) the reaction product of sulfur with said hydrocarbon residue.

2. A composition of matter comprising a rubber 1 selected from the groupconsisting of polybutadiene, butadiene-a-methylstyrene copolymers,butadienevinyltoluene copolymers, butadiene-a-methylvinyltoluenecopolymers, isoprene-styrene copolymers, isoprene-a-methylstyrenecopolymers, isoprene-vinyltoluene copolymers,isoprene-methyl-vinyltoluene copolymers, isoprene-isobutylenecopolymers, isoprene-acrylonitrile copolymers, conjugatedhexadiene-styrene copolymers, conjugated hexadiene a methylstyrenecopolymers, conjugated hexadiene-vinyltoluene copolymers, conjugatedhexadiene-a-methylvinyltoluene copolymers, conjugatedhexadiene-isobutylene copolymers, and conjugated'hexadiene acrylonitrilecopolymers, and an unsaturated polycyclic hydrocarbon residue containingconjugated oleflnic unsaturation and produced by reacting an oleflnichydrocarbon in the presence of liquid hydrogen fluoride at a temperatureof from about 0 to about 150 ,C., separating the resultant reactionproduct into a hydrocarbon layer and a hydrogen fluoride layer,recovering a substantially fluorine-free hydrocarbon material from saidhydrogen fluoride layer, removing from said substantially fluorine-freehydrocarbon material the hydrocarbons boiling below about 150 C. toleave said residue.

- 3. A composition of matter comprising a rubber selected from the groupconsisting of polybutadiene, butadiene-a-methylstyrene copolymers,butadiene-vinyltoluene copolymers, butadiene a methylvinyltoluenecopolymers, isoprene-styrene copolymers, isoprene-a-methylstyrenecopolymers, isoprene-vinyltoluene copolymers,"isoprene--methylvinyltoluene copolymers, isoprene-isobutylenecopolymers, isopreneacrylonitrile copolymers, conjugated hexadienestyrene-copolymers, conjugated hexadiene-amethylstyrene copolymers,conjugated hexadienevinyltoluene copolymers, conjugated hexahydrogenfluoride at a temperature of from about 30 to about 150 0., separatingthe resultant reaction product into a hydrocarbon layer and a hydrogenfluoride layer, recovering a substantially fluorine-free hydrocarbonmaterial from said hydrogen fluoride layer, removing from saidsubstantially fluorine-free hydrocarbon material the hydrocarbonsboiling below about 150 C. to

leave said residue.

4. A composition of matter comprising a rubber selected from the groupconsisting of polybutadiene, butadiene-a-methylstyrene copolymers,butadiene-vinyltoluene copolymers, butadiene a methylvinyltoluenecopolymers, isoprene-styrene copolymers, isoprene-a-methylstyrenecopolymers, isoprene-vinyltoluene copolymers,isoprene-a-methylvinyltoluene copolymers, isoprene-isobutylenecopolymers, isopreneacrylonitrile copolymers, conjugatedhexadienestyrene copolymers, conjugated hexadiene-amethylstyrenecopolymers, conjugated hexadienevinyltoluene copolymers, conjugatedhexadiene-a-methylvinyltoluene copolymers, .conjugatedhexadlene-isobutylene copolymers, and conjugated hexadiene-acrylonltrilecopolymers, and from about 5 to about 30% by Weight of a plasticizercomprising essentially an unsaturated polycyclic oleflnic hydrocarbonmixture boiling above about 150 C. and produced by reacting an oleflnichydrocarbon having at least four carbon atoms per molecule with liquidhydrogen fluoride at a temperature oi from about to about 150 C.

5. A composition or matter comprising a rubber selected from the groupconsisting or polybutadiene, butadiene-a-methylstyrene copolymers,butadiene-vinyltoluene copolymers, butadiene a methylvinyltoluenecopolymers, isoprene-styrene copolymers, isoprene-a-methylstyrenecopolymers, isoprene-vinyltoluene copolymers,isoprene-a-methylvinyltoluene copolymers, isoprene-isobutylenecopolymers, isopreneacrylonitrile copolymers, styrene copolymers,conjugated hexadiene-amethylstyrene copolymers, conjugatedhexadiene-vinyltoluene copolymers, conjugatedhexadiene-c-methylvinyltoluene copolymers, conjugatedhexadiene-isobutylene copolymers, and conjugated hexadiene acrylonitrilecopolymers, and a hydrocarbon plasticizer oil boiling from about 150 toabout 450 0., having an average molecular weight of from about 250 toabout 1000, an average bromine number of from about 120 to about 200,"an average number 01' double bonds per molecule of more than 2 and lessthan 5, a density of from about 0.85 to about 0.95, and a carbon tohydrogen atomic ratio or about 1:1.7.

6. The composition defined in claim further characterized in that therubber comprises polybutadiene. 4

7. The composition defined in claim 5 further characterized in that therubber comprises a copolymer of butadiene and a vinyltoluene.

8. The composition defined in claim 5 further characterized in that therubber comprises a copolymer of isoprene and isobutylene.

9. The composition defined in claim 5 further conjugated hexadiene- 16characterized in that the rubber comprises a copolymer of isoprene andvinyltoluene.

10. The composition defined in claim 5 further characterized in that therubber comprises a copolymer of isoprene and styrene.

11. A co-vulcanized mixture of a rubber-like butadiene homopolymer and aplasticizer oil, the latter comprising essentially an unsaturatedpolycyclic olefinic hydrocarbon residu produced by reacting a normallyliquid monooleflnic hydrocarbon in the presence or liquid hydrogenfluoride at a temperature or from about 0 to about C., separating theresultant reaction product into a hydrocarbon layer and a hydrogenfluoride layer, recovering a substantially fluorinefree hydrocarbonmaterial from said hydrogen fluoride layer, removing from. saidsubstantially fluorine-free hydrocarbon material the hydrocarbonsboiling below about 150 residue.

12. A co-vulcanized mixture of a rubber-like butadiene-vinyltoluenecopolymer, and a plac ticizer oil, the latter comprising essentially anunsaturated polycyclic oleflnic hydrocarbon residue produced by reactinga normally liquid monooleflnic hydrocarbon in the presence of liquidhydrogen fluoride at a temperature or from about 0 to about 150 C.,separating the resultant reaction product into a hydrocarbon layer and ahydrogen fluoride layer, recovering a substantially fluorine-freehydrocarbon material from said hydrogen fluoride layer, removing fromsaid substantially fluorine-free hydrocarbon material the hydrocarbonsboiling below about 150 C. to leave said residue.

13. A co-vulcanized mixture of a rubber-like isoprene-isobutylenecopolymer, and a plasticizer oil, the latter comprising essentially anunsaturated polycyclic olefinic hydrocarbon residue produced by reactinga normally liquid monoolefinic hydrocarbon in the presence of liquidhydrogen fluoride at a temperature of from about 0 to about 150 C.,separating the resultant reaction product into a hydrocarbon layer and ahydrogen fluoride layer, recovering a substantially fluorineireehydrocarbon material from said hydrogen fluoride layer, removing fromsaid substantially fluorine-free hydrocarbon material the hydrocarbonsboiling below about 150 C. to leave said residue.

14. A co-vulcanized mixture of a rubber-like isoprene-vinyltoluenecopolymer, and a plasticizer oil, the latter comprising essentially anunsaturated polycyclic oleflnic hydrocarbon residue produced by reactinga normally liquid monooleflnic hydrocarbon in the presence of liquidhydrogen fluoride at a temperature of from about 0 to about 150 (2.,separating the resultant re action product into a hydrocarbon layer anda hydrogen fluoride layer, recovering a substantially fluorine-freehydrocarbon material from said hydrogen fluoride layer, removing fromsaid substantially fluorin -free hydrocarbon material the hydrocarbonsboiling below about 150 C. to leave said residue.

15. A co-vulcanized mixture of a rubber-like isoprene-styrene copolymer,and a plasticizer oil, the latter comprising essentially an unsaturatedpolycyclic oleflnic hydrocarbon residue produced by reacting a normallyliquid monooleflnic hydrocarbon in the presence of liquid hydrogenfluoride at a temperature of from about 0 to about 150 C., separatingthe resultant reaction product into a hydrocarbon layer and a hydrogenfluoride layer, recovering a substantially fluorine-tree hy- C. to leavesaid drocarbon material from said hydrogen fluoride layer, removing fromsaid substantially fluorinefree hydrocarbon material the hydrocarbonsboiling below about 150 C. to leave said residue.

16. A co-vulcanized mixture of a rubber-like butadiene homopolymer,sulfur, and a plasticizer oil, the latter comprising essentially anunsaturated polycyclic olefinic hydrocarbon residue produced by reactinga normally liquid monooleflnic hydrocarbon in the presence of liquidhydrogen fluOride at a temperature of from about to about 150 C.,separating the resultant reaction product into a hydrocarbon layer and ahydrogen fluoride layer, recovering a substantially fluorinefreehydrocarbon material from said hydrogen fluoride layer, removing fromsaid substantially fluorine-free hydrocarbon material the hydrocarbonsboiling below about 150 C. to leave said residue.

17. A co-vulcanized mixture of a rubber-like butadiene-vinyltoluenecopolymer, sulfur, and a plasticizer oil, the latter comprisingessentially an unsaturated polycyclic oleflnio hydrocarbon residueproduced by reacting a normally liquid monooleflnic hydrocarbon in thepresence of liquid hydrogen fluoride at a temperature of from about 0 toabout 150 C., separating the resultant reaction product into a.hydrocarbon layer and a hydrogen fluoridelayer, recovering asubstantially fluorine-free hydrocarbon material from said hydrogenfluoride layer, removing from said substantially fluorine-freehydrocarbon material the hydrocarbons boiling below about 150 C. toleave said residue.

18. A co-vulcanized mixture of a rubber-like isoprene-isobutylenecopolymer, sulfur, and a plasticizer oil, the latter comprisingessentially an unsaturated polycyclic oleflnic hydrocarbon residueproduced by reacting a normally liquid monooleflnic hydrocarbon in thepresence of liquid hydrogen fluoride at a temperature of from about 0 toabout 150 C., separating the resultant reaction product into ahydrocarbon layer and a hydrogen fluoride layer, recovering asubstantially fluorine-free hydrocarbon material from said hydrogenfluoride layer, removing from said substantially fluorine-freehydrocarbon material the hydrocarbons boiling below about C. to leavesaid residue.

19. A co-vulcanized mixture of a rubber-like isoprene-vinyltoluenecopolymer, sulfur, and a plasticizer oil, the latter comprisingessentially an unsaturated polycyclic oleflnic hydrocarbon residueproduced by reacting a normally liquid monoolefinic hydrocarbon in thepresence of liquid hydrogen fluoride at a temperature of from about 0 toabout 150 C., separating the resultant reaction product into ahydrocarbon layer and a hydrogen fluoride layer, recovering asubstantially fluorine-free hydrocarbon material from said hydrogenfluoridelayer, removing from said substantially fluorine-freehydrocarbon material the hydrocarbons boiling below about 150 C. toleave said residue.

20. A co-vulcanized mixture of a rubber-like isoprene-styrene copolymer,sulfur, and a plasticizer oil, the latter comprising essentially anunsaturated polycyclic oleflnic hydrocarbon residue produced by reactinga normally liquid monooleflnic hydrocarbon in the presence of liquidhydrogen fluoride at a temperature of from about 0 to about 150 C.,separating the resultant reaction product into a hydrocarbon layer and ahydrogen fluoride layer, recovering a substantially fluorine-freehydrocarbon material from said hydrogen fluoride layer, removing fromsaid substantially fluorine-free hydrocarbon material the hydrocarbonsboiling below about 150 C. to

leave said residue.

HERMAN S. BLOCH.

No references cited.

1. A COMPOSITION OF MATTER COMPRISING A RUBBER SELECTED FROM THE GROUPCONSISTING OF POLYBUTADIENE, BUTADIENE-A-METHYLSTYRENE COPOLYMERS,BUTADIENE-VINYLTOLUENE COPOLYMERS, BUTADIENE-AMETHYLYVINYLTOLUENECOPOLYMERS, ISOPRENE-STYRENE COPOLYMERS, ISOPRENE-A-METHYLSTYRENECOPOLYMERS, ISOPRENE-VINYLTOLUENE COPOLYMERS,ISOPRENEA-METHYLVINYLTOLUENE COPOLYMERS, ISOPRENE-ISOBUTYLENECOPOLYMERS, ISOPRENE-ACRYLONITRILE COPOLYMERS, CONJUGATEDHEXANDIENE-STYRENE COPOLYMERS, CONJUGATED HEXADIENE-A-METHYLSTYRENECOPOLYMERS, CONJUGATED HEXADIENE-VINYLTOLUENE COPOLYMERS, CONJUGATEDHEXADIENE-A-METHYLVINYLTOLUENE COPOLYMERS, CONJUGATEDHEXADIENE-ISOBUTYLENE COPOLYMERS, AND CONJUGATED HEXADIENEACRYLONITRILLE COPOLYMERS, AND A PLASTICIZER SELECTED FROM THE GROUPCONSISTING OF: (1) AN UNSATUREATED POLYCYCLIC HYDROCARBON RESIDUECONTAINING CONJUGATED OLEFINIC UNSATURATION AND PRODUCED BY REACTING INTHE PRESENCE OF LIQUID HYDROGEN FLUORIDE AT A TEMPERATURE OF FROM ABOUT0* TO ABOUT 150* C. AT LEAST ONE ALIPHATIC HYDROCARBON SELECTED FROM THEGROUP CONSISTING OF ISOPARAFFINIC AND OLEFINIC HYDROCARBONS, SEPARATIGNTHE RESULTANT REACTION PRODUCTS INTO HYDROCARBON LAYER AND A HYDROGENFLUORIDE LAYER, RECOVERING A SUBSTANTIALLY FLUORINE-FREE HYDROCARBONMATERIAL FROM SAID HDYROGEN FLUORIDE LAYER, AND REMOVING FROM SAIDLAST-NAMED MATERIAL THE HYDROCARBONS BOILING BELOW ABOUT 150* C. TOLEAVE SAID RESIDUE. AND (2) THE REACTION PRODUCT OF SULFUR WITH SAIDHYDROCARBON RESIDUE.